Search Documents

By N. J. Grant, B. C. Giessen, R. Koch

The system Nh-Ir was investigated over the complete concentration range by metallography and X-my techniques, using forty one alloys. The solubility limits of terminal and intermediate phases and the solidus temperatures were determined. Five intermediate phases were found: a Nb3Ir, cubic, Cr3O type; tetragonal, ofecr thorhomhic, isostruc-turn1 with (ta-Rh); and a Nhlr3. cubic, AuCu, type. a Nb3lr and a Nbfr3 melt congruently; three eutectic and three pentectic reactions occur. The phase diagram of the Nb-Ir system had not been fully treated in the literature; only surveys of intermediate phases were found.1"5 In this study, the details of the phase boundaries were investigated as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS The experimental procedures such as arc melting of powder compacts, heat treatments, solidus measurements, X-ray, and metallographic observation were identical with those used in the work on the Nb-Rh phase diagram.&apos; They will therefore not be repeated here except where the conditions differed. The purity of the niobium powder was as stated in Ref. 6; the iridium powder of 99.9+ pct purity from J. Bishop and Co., Malvern, Penn., did not contain impurities exceeding 100 ppm, except rhodium (200 ppm). The melting points and vapor pressures of both elements are very similar. This fact contributed to a very small weight loss on melting and facilitated preparation of homogeneous alloys. As shown in Ref. 6 for Nb-Rh, no oxygen pick-up exceeding 200 ppm had to be considered; this was regarded as valid also for Nb-Ir. A total of forty one alloys were used in the determination of the phase diagram; their concentrations are shown in Fig. l, which presents the phase diagram. The concentration limits as determined by the weight-loss method averaged <0.2 at. pct, and never exceeded 0.5 at. pct. Heat treatments were carried out as described in Ref. 6. Depending on the concentration, only tantalum, tungsten, or iridium containers were employed, avoiding oxide crucibles altogether. Alloys from 0 to 25 and from 65 to 100 at. pct Ir were homogenized at 2095°C for 15 hr, intermediate compositions from 25 to 65 at. pct Ir for 65 hr at 1780°C. A typical annealing-time schedule is presented in Table I. Solidus points were measured as described in Ref. 6 with the modification that samples rich in niobium were held between pieces of tantalum foil and samples of high iridium concentrations were held between rhenium platelets or in iridium wire. After each run it was ascertained metallographically that no reaction with the holder had occurred. Rhenium was selected as holder material after it had been shown in separate tests that the melting points of Re-Ir alloys rise continuously from 2440°C. Metallographic examination was carried out as described in Ref. 6, and the same procedure and etchants were used successfully. While metallographic discrimination between a Nb3lr and o was easily possible, X-ray diffraction was necessary to separate al and ct2. X-ray powder patterns were taken and evaluated as for Nb-Rh6 yielding the error limits indicated in Table 111, to be introduced later. For the determination of the invariant reactions and phase boundaries, the same techniques as for Nb-Rh6 applied. The general accuracy of invariant concentrations is regarded as somewhat higher than for Nb-Rh due to the small slope of most solvus lines.

Jan 1, 1964

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By C. A. Hartinagel

During 1941, the total production of crude oil in New York state was 5,185,000 bbl. This represents a small increase over the average for the past five years. From 1921, when the annual production of the state amounted to only 988,000 bbl., there was a regular annual increase in production (excepting one or two years) until the 5,000,000-bbl. mark was reached in 1937, After more than 20 years of oil recovery by flooding methods, it was generally believed, until a few months ago, that the rate of production was nearly at its peak and within a few years the fields would experience a gradual decline as the thicker sands became exhausted and the thinner ones could be worked only at increasing costs. As a result of the present emergency, however, unusual efforts are being made, in spite of higher costs of operation, to increase the output of Pennsylvania grade oil, to which the New York product belongs. Since most of any increased production would be obtained by flooding, and since floods travel slowly, no large increase in production can be expected for some months to come. During the first year, 10 or 15 per cent increase could be obtained, but maximum production, an increase of perhaps 40 per cent, could not be expected until some time during the second or third year. In the Allegany fields, which account for two thirds of the state&apos;s oil production, 1246 wells, including water-intake wells, were drilled during the year; 390 more than in the preceding year and 590 more than in 1939. It is evident that much of the best oil territory has already been developed. As producers move toward edge properties and thinner sands, returns will be smaller, whereas costs remain the same or, under war conditions, become higher. It is estimated that at least 60 million barrels of oil is in sight and will be produced from the thicker sands by present recovery methods. In the thinner sands and edge properties, some 35 million additional barrels can be produced at a profit only if prices become higher. In view of the fact that there is little hope of finding new oil pools in New York, one of the future problems of the oil producer will be to obtain adequate returns for increased production costs. The year started with a posted price of $2.15 per barrel of crude. There were five successive price increases until the high of the year was reached at $2.98 on Aug. 14. Eight days later the Office of Price Administration directed that the price be reduced to the June level of $2.75 a barrel, which remained in effect to the end of the year. With rising costs of operation, it is feared that many of the smaller properties cannot continue production unless the Federal price cut is revoked. During the year, Allegany Refiners Inc., a local enterprise founded in 1933, with plant at Bolivar, western Allegany County, increased its refining capacity from 1000 to 1500 bbl. daily. At the same time equipment was added to make the plant a complete lubricating-oil refinery, including facilities for the refining of wax into the finished product. Previous to the enlargement, it was necessary to sell the wax

Jan 1, 1942

By H. H. Rachford, W. P. Schultz

The use of computing machines to solve physical problems has made it imperative to represent physical data in a form computing machines can use. Although curve-fitting is an old and well-practiced art, there still seems to be some interest in questions regarding what methods can be used and why. Even though there are many good references on this subject, it may be of some value to discuss a particular method which has been found to be useful, and to make available the associated tables for its use in the hope that there can be saved a few of the tedious hours necessary to reduce many of the suggested methods to practice. Although a very brief discussion of the mathematical background of the tables is included immediately below, those interested only in their use can skip directly to the section on Use of the Tables. Direct Fit of a Set of Points A frequently encountered problem is: Given data which can be represented by a smooth curve +(x), to find an easy-to-evaluate function F(x), with only a few coefficients, which is a good approximation of +(x) on the interval 0 5 x 5 x,,. Consider F(x) as a linear combination of m + 1 arbitrary, single-valued, continuous, linearly independent functions, f,(x), Ff.r) = a,f,,(x) + a,f,(x) + . . . -+ aifi(x) + If the value of Q(x) is known or can be read from the curve at the points xj: +(x,), +(x,), . . . +(xj) . . . +(x.), and if n = m, then all the coefficients of F(x) can be determined, and F(x,) — +(x,) = 0 for j =. 0, 1, . . . n. This follows from the solution of the set of linear simultaneous equations. +(x<.) = aofu(x,) + aJI(x0) + . . . + a,,f,,(x,) =a, = f,,(x,) + a,f,(x,) + . . . + a,f,,(x,) +(x,,) = a,,f,(x,,) + a,f,(x,) + ... + a,,f.,(x,,) ...........(2) for the coefficients ai. Although the set a, from the solutions of the set of Equations 2 yields an fix) which gives an exact value of $(x,) for the n + 1 points, there is no restraint on ~(xj in the interval xi < x < xj+,. Indeed, if the points +(x,) are not sufficiently smooth, very serious differences may arise between F(x) in the interval and the smooth curve +(x). Least-Squares Fit It has been suggested&apos; that if n is made to exceed m, and the set a, is found to minimize the function the function F(x) is much less sensitive to small errors in +(xi), and usually provides a much better fit to the smooth function +(x). This is known as the best fit in the sense of the least-squares error. To minimize $, set £ = 0,i = 0,1,... iTi,.....(3) The m + 1 equations from Equation 3 are k—n k=n a.^p /,,(a) f,(xt) + a, X A: = 0 k=O k = n k = n k=0 k=0 +(x.) f,(x,),............(4) one equation being obtained for each i = 0, 1, . . . m. Inasmuch as the arbitrary functions f(x) may be evaluated for x,, k = 0, 1, . . . n, and the +(x,) are known values of the curve to be fitted, the simultaneous Equations 4 may be solved for the set a,. Particular Functions Given the functions fi(x) and the set +(xj), the solutions for require evaluating a number of sums of products as well as the solution of an m + 1 order set

Jan 1, 1956

By Sven Fornander

An account is given of the way in which a new process for desulphurization of hot metal is carried out at a Swedish blastfurnace plant. In the process powdered burnt lime is used as a desulphurizing agent in a rotary furnace. Results are given. IN a paper by Kalling et al.* the fundamentals of a new process for desulphurization of hot metal using powdered burnt lime as a desulphurizing agent were outlined. The purpose of the present paper is to give a brief account of the way in which this process is being carried out in practice by Surahammars Bruks AB, Sweden, and of the results obtained. + The hot metal from the blast furnace is tapped into a ladle of 15 tons capacity and transferred to a rotary furnace, a simplified drawing of which is given in Fig. 1. The rotary furnace has a total length of about 160 in. and an outside diameter of the rings of about 130 in. The furnace is in a horizontal position, with its rings placed on four rollers, and can be rotated by a driving mechanism at various speeds of up to 34 rpm. The rotary furnace and its driving mechanism were designed and constructed at Surahammar. The hot metal is charged into the rotary furnace through the opening to the left in Fig. 1. See Fig. 2. An addition is then made to the furnace consisting of finely ground burnt lime amounting to 2 pct of the weight of the hot metal as well as 0.5 pct of coke breeze. After the additions are made, the furnace is sealed to the atmosphere by means of two lids and set in rotary motion at a rate of 34 rpm. The sulphur in the hot metal is rapidly absorbed by the lime added, the time of treatment needed is normally 30 min. The process is then stopped, the lid is removed, and the furnace is lifted up by a crane and used as a tilting ladle for pouring the metal into the pig-iron molds, Fig. 3. Process Metallurgy The hot metal charged into the rotary furnace has a composition which usually lies within the following limits: C, 3.70 to 4.10 pct; Si, 0.80 to 1.80; Mn, 0.40 to 0.80; P, 0.025 to 0.030; and S, 0.060 to 0.200. Figs. 4 and 5 give examples of the changes in hot metal composition taking place during the treatment in the rotary furnace. As will be seen from the diagrams, the sulphur content of the metal decreases very rapidly during the first 10 min of treatment from about 0.100 to about 0.020 pct S. During the following 20 min, the sulphur content goes down slowly to about 0.005 pct S. The carbon and silicon contents of the metal decrease by about 0.10 pct each during the treatment. The manganese and phosphorus contents remain unchanged. Thus, if the process is started with an iron of the composition given above, the finishing composition of the metal usually lies within the following limits: C, 3.60 to 4.00 pct; Si, 0.70 to 1.70; Mn, 0.40 to 0.80; P, 0.025 to 0.030; and S, 0.002 to 0.020. The chemical reaction taking place during the process can be written:

Jan 1, 1952

By T. G. Digges, M. R. Achter

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By F. M. Lewis, E. C. Johnson

Used as a classifier in a plant expanding capacity or changing to closed-circuit operation, the liquid-solid cyclone offers the advantage of being adaptable to existing conditions. This paper presents the costs involved and experience gained from operating a unit of this kind. BY now application of the liquid-solid cyclone to various classification problems in the chemical and metallurgical fields is more or less familiar. A less publicized application receiving wider consideration as time goes on is its use as a classifier in closed-circuit grinding operations. This paper presents the costs involved and the experience gained from operating a unit of this kind. In May 1951 the Tennessee Copper Co. installed in its London mill at Copperhill, Tenn., a liquid-solid cyclone in closed circuit with a 6x12-ft ball mill. The circuit in which this cyclone is used is the regrind or secondary grinding circuit of a copper flotation plant. Originally it consisted of a 7x1-ft conical ball mill in closed circuit with a bowl classifier. Changes made in the primary grinding circuit of the mill necessitated a regrind circuit of greater capacity. The bulk concentrate to be ground was raised from 900 or 1000 tpd to 1200 or 1300 tpd, and to accommodate this increase a 6x12-ft ball mill which had been in the primary grinding circuit was moved into the regrind circuit. When this was done it was found that the classifier was too small to give efficient operation. Space in the plant was at a premium, and since use of the cyclone offered considerable economy the installation shown in Figs. 1-3 was made. The unit installed is a 24-in. diam cyclone classifier with a 20" cone angle. Diameter of the vortex finder is 8 in., the feed entrance area 20 sq. in. Maximum diameter of the adjustable apex valve is 6 in. and minimum diameter approximately 3.5 in. To refer again to Figs. 1 and 2, the cyclone* is mounted motor. It is charged with 18 tons of 1-in. balls. The overflow, or fines, passes by gravity directly to the copper flotation plant. The ball mill discharge and the new feed combine in a sump from which they are sent to the cone by an 8x6 SRL pump at a rate of 497 gpm. Pressure at the cyclone is 5 psi. For reasons dictated by the nature of the ore treated, particularly the bonding of fine grains of chalcopyrite to pyrrhotite, the froth from the second cell of the copper rougher circuit is returned to the regrind mill. This flow, which somewhat complicates the standard closed-circuit calculation, is seen in Fig. 1 to be 156 tpd of solids. This combines with the cyclone classifier underflow to constitute the ball mill feed. The requirement of the regrind product is that it be 77 to 80 pct —200 mesh. The liquid-solids cyclone operating in conjunction with the 6x12-ft mill adequately met this requirement. Of primary importance is the fact that this arrangement provided sufficient classification capacity to replace the undersized classifier and was capable of building up a circulating load to 87 pct, large enough to give an efficient grind. In this instance the circulating load is taken as the ratio of sands to new feed. Any comparison of performance between this liquid-solid cyclone and the replaced classifier would of course be unfair, since the bowl classifier was

Jan 1, 1955

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.&apos; The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By U. F. Kocks

SINGLE slip and a single parallel array of edge dislocations have been obtained in silicon single crystals by homogeneously bending them in a four-point dead-loading device at 1000°C around the [211] axis with [253.] as the tensile axis which encloses an angle of 40° with the glide plane. Other orientations or lower temperatures proved unsuitable. The homogeneity of the bending was checked by the method shown in Fig. 1. The chemically polished specimen was exposed to parallel light from a microscope-stage lamp. The sharpness of the focus of the reflected light is an approximate measure of the circularity of the sample. This method permitted the determination of the actual radius of bent specimens within 10 pct accuracy. The etching solution developed to show up dislocations consisted of the following volume parts: 2 HF, 1 HNO,, 2 CH,COOH, 1 a solution of 5 wt pct of CuNO, in water (Rosi&apos;). The acetic-acid content was adjusted to produce fine well-defined etch-pits in about 2 min at room temperature. The effectiveness of the etch did not depend on the crystal-lographic orientation of the face etched. The number of etch pits produced after a given deformation was checked in the usual way against the Cahn formula&apos; and showed good agreement. As it is to be expected from the orientation of the primary system there are slip steps on the top and bottom faces but not on the side faces (perpendicular to the bending axis), whereas etch pits appear on the side faces but not on the top and bottom faces. This is different only for occasional dislocations of a secondary glide system. All the micrographs included have been taken in places where the most of secondary glide could be seen. From this it is evident that in the homegeneously deformed region the number of secondary dislocations was less than 1 in 1000 of the primary type. Dislocation Distribution—A series of tests with varying amounts of deformation is shown in Figs. 2(a-c). An observation that can readily be made from these pictures is that the linear density of dislocations within slip lines is relatively constant and independent of the amount of deformation. "Slip line" in this context is understood to mean a line that is a straight connection of individual etch pits. The heavily pitted bands which can be seen in each of these three pictures may be resolved fairly definitely, at higher magnifications, into many "slip lines" the distance between them being of the order of 0.5p The distance between dislocations in slip lines is of the order of 2p and it is also fairly constant in going from the neutral zone outward. The higher over-all dislocation density in the outer regions of any sample and the higher total number in a more heavily deformed sample, are effected by a larger number of "slip lines." The relative constancy of the dislocation distance within an individual slip line is surprising. The absence of pile-ups" may imply, if there is no rear- rangement on unloading," that there are no substantial obstacles to slip in this case. It seems that the equilibrium distribution of the dislocations in each active slip plane under the higher external stress on

Jan 1, 1959

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura&apos; have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By James Kemp

PostScript to a paper presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 129 to 154. The writer looked over the quarry with care in the search for fossils, having in mind shells or corals of fairly large size. In the brilliant summer sunshine, none were observed on the glaring white ledges. The impression was gained that none were present and the statement to this effect was made in the edition of this paper published in the Bulletin&apos; of the Institute for February, 1915, p. 136. On closer examination in the laboratory it has been discovered that the limestone itself is made up of minute organisms, which are clearly revealed by microscopic examination of thin sections. The principal component of the rock is a small foraminifer, 0.1 to 0.3 in. (2.5 to 7 mm.), of the genus Orbitoides, presumably an Oligocenic form. Figs. 1 and 2. illustrate it. The accompanying description has been kindly summarized by Marjorie O&apos;Connell, M. A., Curator in Paleontology in Columbia University, who first detected the evidences of organisms in the rock. Orbitoides kempi O&apos;CONNELL N. SP.1 The foraminiferan which makes up the Seboruco limestone is an Orbitoides of a Species new to North America. The only Orbitoides heretofore described from this country is 0. mantelli from the lower Oligocenic of the Gulf States. This form from Cuba, then, so different in all of its characteristics from the 0. mantelli, is of great interest as perhaps forming a basis of correlation over wide areas. The most closely related Species is 0. dispansa Sowerby, which occurs in the Nummulite limestone of the Eocenic of the Bavarian . Alps, in the Priabona beds of the lower Oligocenic of Massano, and elsewhere in Italy, as described by Gümbel.2 The age of the limestone in Cuba would thus Seem to be of upper Eocenic or lower Oligocenic age, probably the latter. The fossil has the form of a sphere Surrounded by a wavy rim of horizontal extent, the whole resembling two flat-brimmed, round-crowned hats placed base to base. The total extent of the Shell ranges up to 7+ mm., while the thickness of the central sphere is 2.5 mm. in one of the largest individuals. Like all of the other Species of Orbitoides, this form begins with a Single layer of chambers which multiply in one plane and assume a circular outline; but it is in the subsequent growth that the distinguishing specific characters appear, for the chambers at the central portion of the shell increase more rapidly than do those near the periphery and in consequence a Swelling is produced which finally gives the Spherical form which is so characteristic. The rim, on the other hand, shows little chamber-increase and remains thin. This is clearly Shown in the sections figured, where the central row of larger chambers forms the equatorial zone. Radiating from this row, in section, there appear, a number of solid cones alternating with broad reticulated ones. The solid cones mark the more dense structure forming the walls surrounding the reticulated or chambered cones. These appear upon the Surface as distinct pits, whereas the solid part appears as raised walls.

Jan 7, 1915

By Shiou-Chuan Sun

SHIOU-CHUAN SUN (author&apos;s reply).-Thanks are extended to Professor Hassialis for his recognition of the usefulness of a new tool, the cataphoretic cell, as an adjunct to the bubble machine and the abstraction test. His questions concerning adsorption, dielectric constant, floatability, activation, and depression are interesting and worthy of discussion. I According to Mueller,28 it is questionable that any of the present formulas gives absolute values of zeta potentials which are completely accurate. The problem is further complicated by the question" of whether the "dielectric constant" has any meaning at all for such a microscopically thin layer. With these in mind, the results in this paper should be considered in the relative sense as a first approximation and not as absolute quantities. Adsorption Referring to item a of Fig. 8, the dielectric constant and the viscosity of the xanthate solutions are the same for galena, sphalerite and quartz. If dielectric constant and viscosity (but not the adsorption) were the first-order variable of the cataphoretic system, as claimed by Professor Hassialis, then the magnitudes of zeta coefficient of galena, spha)erite and quartz would have been similar to each other. These are not. The big difference of zeta coefficient of these three minerals in the same xanthate solutions is not altogether unjustified to be attributed to their difference in adsorption of xanthate ions. This is supported by the results of chemical abstraction tests reported by Ince.14 Again, the big difference of zeta coefficient between wollastonite, calcite, and fluorite in the same laurylamine hydrochloride solutions (p. 118, Figs. 58, 59, and 60 of ref. r5) also indicates that the cataphoretic system is not governed chiefly by the dielectric constant. Beside the data shown in Fig. 8, other experimental evidences15 which support the idea of correlation between adsorption and zeta coefficient are: (I) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of various concentrations of sodium cyanide, (2) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of constant concentration of copper sulphate at different pH values, and (3) there is a qualitative parallelism between zeta coefficient curve and chemical abstraction curve of quartz in solutions with constant concentration of barium chloride at different pH values. The above mentioned experimental results are generally in agreement with Gouy&apos;s double layer theory,1-5 and support this idea that the concentration and the kind of ions adsorbed at the mineral surface and in the adjacent surrounding liquid chiefly govern the electrokinetic phenomena. Dielectric constant and viscosity of the liquid medium may be of somewhat lesser importance. It follows that the correlation between the coefficient and adsorption as claimed in this paper is justified. Dielectric Constant The term "dielectric constant " was first introduced into the electrokinetic equations by Perrin.30 In a footnote of his publication he states that Holmheltz has forgotten to include the dielectric constant. The conversion of the moment29 to the zeta potential involves an additional difficulty and confusion not involved for the moment, namely, assigning a value to the dielectric coefficient. This is conventionally assumed to be constant and equal to the dielectric constant of the bulk liquid. 21 The published literature 10, 12 indicates that the values of dielectric constant for dilute chemical solutions have been assumed as those of pure water.

Jan 1, 1947

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O&apos;Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By O. N. Carlson, D. G. Alexander

THE hardness anisotropy of metals and alloys has been of increasing interest in recent years but silicon ferrite,1 niobium,2 and tungsten3,4 are the only bcc metals about which this type of information has been reported. This investigation was carried out on vanadium and chromium single crystals in an effort to determine to what degree the hardness variations observed in these metals are due to orientation effects and to compare their behavior with other bcc metals. In earlier work the authors had observed a small angular dependence in the Diamond Pyramid Hardness of single crystalline vanadium on the (100) plane but no anisotropic effects were noted on either the (110) or (111) planes. At the suggestion of R. G. wheeler5 it was decided to investigate this effect in greater detail using the more asymmetric Knoop indentor. The vanadium metal used in the study was prepared by the aluminothermic reduction of V2O5 followed by electron beam melting.6 The principal analyzed impurities were 230 ppm C, 230 ppm O, 65 ppm N, 90 pprn Al, Cr not detected, 50 ppm Fe, 60 ppm Ni, and 200 ppm Si. The chromium was an iodide-refined product obtained from the Chromalloy Corporation. Analysis of this material showed the following amounts of impurities present: 10 ppm C, 9 ppm O, 2 ppm N, 0.4 ppm H, 3 ppm Al, 2 ppm Ca, 2 ppm Cu, 20 ppm Fe, 1 ppm Mg, 0.3 ppm Mn, 1 ppm Mo, 3 ppm Ni, 10 ppm Si, and 1 ppm V. Single crystals of both metals about 1 cm in diam and 10 cm in length were grown by an arc-zone melt- ing technique.7 The chromium crystal was annealed at 1600°C for 6 hr in a purified argon atmosphere to remove any strains or inhomogeneities, but the vanadium was tested in the as-grown condition. The crystals were oriented by the Laue back-reflection method and then sectioned with a spark cutter into individual specimens with a (loo), (110), or (111) plane parallel to the crystal surface. They were mounted in Lucite and carefully ground to a flat surface. The vanadium specimens were then electropolished in a 6 pct perchloric acid-methanol mixture while the chromium specimens were mechanically polished on a Syntron vibratory polisher using an alumina abrasive. The orientation of each crystal was then rechecked by the back-reflection X-ray method. All of them were found to lie within 2 deg of the desired orientation with the exception of the (110)-Oriented chromium crystal which was within 4 deg. Microhardness impressions were taken at 10 deg intervals from the common (110) direction by rotating the crystal in the plane of the crystal surface. A Knoop indentor was used with a 400-g load on the vanadium crystals and an 800-g load on the chromium. The hardness values are averages of 6 impressions and standard deviations were calculated for each set of data. The values reported for the (111) plane of vanadium are based on from 10 to 15 measurements for each point. The microhardness results for vanadium and chromium are plotted as a function of the angular rotation of the long axis of a Knoop indentor from the (110)

Jan 1, 1970

By C. A. Hartinagel

During 1941, the total production of crude oil in New York state was 5,185,000 bbl. This represents a small increase over the average for the past five years. From 1921, when the annual production of the state amounted to only 988,000 bbl., there was a regular annual increase in production (excepting one or two years) until the 5,000,000-bbl. mark was reached in 1937, After more than 20 years of oil recovery by flooding methods, it was generally believed, until a few months ago, that the rate of production was nearly at its peak and within a few years the fields would experience a gradual decline as the thicker sands became exhausted and the thinner ones could be worked only at increasing costs. As a result of the present emergency, however, unusual efforts are being made, in spite of higher costs of operation, to increase the output of Pennsylvania grade oil, to which the New York product belongs. Since most of any increased production would be obtained by flooding, and since floods travel slowly, no large increase in production can be expected for some months to come. During the first year, 10 or 15 per cent increase could be obtained, but maximum production, an increase of perhaps 40 per cent, could not be expected until some time during the second or third year. In the Allegany fields, which account for two thirds of the state&apos;s oil production, 1246 wells, including water-intake wells, were drilled during the year; 390 more than in the preceding year and 590 more than in 1939. It is evident that much of the best oil territory has already been developed. As producers move toward edge properties and thinner sands, returns will be smaller, whereas costs remain the same or, under war conditions, become higher. It is estimated that at least 60 million barrels of oil is in sight and will be produced from the thicker sands by present recovery methods. In the thinner sands and edge properties, some 35 million additional barrels can be produced at a profit only if prices become higher. In view of the fact that there is little hope of finding new oil pools in New York, one of the future problems of the oil producer will be to obtain adequate returns for increased production costs. The year started with a posted price of $2.15 per barrel of crude. There were five successive price increases until the high of the year was reached at $2.98 on Aug. 14. Eight days later the Office of Price Administration directed that the price be reduced to the June level of $2.75 a barrel, which remained in effect to the end of the year. With rising costs of operation, it is feared that many of the smaller properties cannot continue production unless the Federal price cut is revoked. During the year, Allegany Refiners Inc., a local enterprise founded in 1933, with plant at Bolivar, western Allegany County, increased its refining capacity from 1000 to 1500 bbl. daily. At the same time equipment was added to make the plant a complete lubricating-oil refinery, including facilities for the refining of wax into the finished product. Previous to the enlargement, it was necessary to sell the wax

Jan 1, 1942

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.&apos; Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer&apos;s number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By P. R. Sperry, P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the inside texture of highly rolled aluminum and copper strips may be approximately described by four equivalent ideal orientations near (123) [121]. If rolled in reversed passes, the surface texture of copper is also near (123) [121], that of aluminum is (100) [011]. The inside texture of highly rolled brass is (110) [112]. The surface texture is the same, if rolled in reversed passes. The surface texture of all three metals is related to the inside texture, but asymmetrical, if rolled without reversal between passes. MANY previous investigations dealing with the subject of the present work were reviewed by Wassermann.1 Barrett,2 Brick,3 and Richards.&apos; The recent introduction of quantitative methods for pole figure determination by Decker, Asp, and Harker,5 Schulz5 and others made it possible to reinvestigate some of the finer points which the earlier more qualitative photographic methods left undecided. The rolling textures of silver and of 70-30 cartridge brass have been quite consistently characterized by the ideal orientation of (110) parallel to the plane of rolling and [112] parallel to the rolling direction. On the other hand, it has been recognized by several investigators that certain other face-centered cubic metals, such as copper and aluminum, developed rolling textures rather different from that of brass. These textures have been variously described by the following ideal orientations, singly or in combinations with each other: (110 [112]: (112) [111]; (135) [335]; (135) [211], etc. The discrepancies usually have been attributed to the lack of sharpness in the textures and to the attendant difficulty of associating "ideal orientations" with pole figures showing great scatter of orientations. It seemed desirable to investigate by the new quantitative methods to what extent the apparent lack of sharpness may have been brought about by the qualitative methods used previously, rather than by the textures themselves, and to decide, if possible. between the various ideal orientations which have been proposed. Another problem, not satisfactorily settled by earlier investigations. concerns surface textures in rolled metals. For instance, in rolled aluminum the surface texture in some cases appeared to be similar to the texture inside the sheet, whereas in other cases it was reported to be entirely different.&apos; The conditions under which such differences may have arisen, and the possibility of the occurrence of different surface textures in other face-centered cubic metals do not appear to have been examined in detail. The present work was undertaken to investigate the above questions. Some of the results obtained have been described- riefly. Experimental Procedure Specimen Preparation: In the present investigation 2s aluminum, electrolytic tough-pitch copper, and commercial 70-30 brass were used. These materials were available in the form of cold-drawn rods. 1 in. diam for tough-pitch copper and commercial 70-30 brass and 11/2 in. diam for 2s aluminum. The cold-drawn bars were alternately annealed and rolled 30 pct lengthwise in several cycles until a penultimate thickness of 0.500 in. was reached. The intermediate and the penultimate anneals were carried out for 30 min at 380°C with 2s aluminum, and for 30 min at 550°C with 70-30 brass. For tough-pitch copper, the intermediate anneals were 30 min

Jan 1, 1953

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low grade molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported. In the chlorination process, a gaseous mixture of chlorine and oxygen in the volume ratio bf 2:5 has been passed at 1.66 x 10- 5 m3/s for 1800 s over a 0.01 kg batch of molysulfide concentrate at a temperature of 573°K. Most of the molybdenum has been volatilized as molybdenum oxychloride which has subsequently been extracted in water. The molybdenum value from the aqueous solution has been recovered in the form of calcium molybdate (CaO.MoO3) by treatment with calcium chloride (CaCI2). In an alternative processing scheme, the molybdenum rich solution has been treated with an oxidizing agent (K2S20f.J) and allowed to boil to recover a major portion of the molybdenum value in the form of molybdic oxide (MOOS). The spent charge obtained after molysulfide chlorination has been mixed with about 1 wt % sodium chloride and heated at 773K under an oxygen atmosphere. The reacted mass has been water-leached to yield a nickel-copper bearing solution with limited iron. The process liquor appears to be well suited for further processing by known hydrometallurgical recovery processes for nickel and copper. In the conventional process of molybdenum extraction, the molysulfide concentrate (-59% Mo) is first subjected to roasting to produce molybdic oxide. The oxide is then further processed in sequential steps involving vacuum distillation, ammonia leaching, and calcination to higher purity prior to hydrogen reduction to metal. In India there is at present some small tonnage production of molysulfide concentrate from a byproduct recovery plant of the M/s. Uranium Corp. of India Ltd. (M/s UCIL), Bihar. Efforts are being made at this laboratory to process the low grade fraction of the concentrate which contains sulfides of copper, nickel, and iron; quartz; and chlorites. Here, the conventional routes involving roasting and vacuum distillation appear unsuitable to produce an acceptable quality of molybdic oxide at high recoveries. Formation during roasting molybdates of some of the impurities present in the sulfide concentrate make subsequent vacuum distillation less efficient. In view of these problems, in earlier work reported from this laboratory the low grade concentrate has been processed hydrometallurgically to P. produce calcium molybdate. Starting from this molybdenum intermediate, processes have also been developed for the production of molybdenum and ferromolybdenum. Chlorination as an alternative to roasting for metal sulfides has been drawing considerable interest. The high reactivity of chlorine, the relatively low temperature of operation, the suitability of application to low grade resources, the convenience of recovering sulfur in non-polluting form, and the purity of chlorides which are separated by distillation all favor chlorination. In recent years, considerable work has been reported on the chlorination of common metal sulfides. In the field of molybdenum extraction from its sulfide resource, use of chlorination technology has been rather limited. Senderoff and Labrie3 were the first to chlorinate molysulfide concentrate with elemental chlorine at about 823°K to molybdenum pentachloride for use in the electrolytic preparation of molybdenum. The only other reported work, by Haver, Uchida and Wong, involved reaction between molysulfide and chlorine at 673°K to recover sulfur. The reaction products were, however, identified as molybdenum pentachloride and sulfur monochloride.

Jan 1, 1979

By W. A. Stickney, J. W. Town

Tests demonstrated that aqueous solutions of sodiu~n sulfide would dissolve over 95 pct of the cinnabal- in 5 pct Hg flrotation concentrates and 60 to 90 pct of the cinnabav in low-grade ol-es. Double-leach tests showed that potassiutn sulfide would dissolve 90 pct of the avsenic sulfide in Hg-As satnples and only 1 to 10 pct of the Hg; the sodium sulfide would then dissolve 80 to 90 pct of the rernaining Hg and 30 to 70 pct of the vemaining As. 1 HIS paper describes the extraction, by alkaline sulfide solutions, of mercury from cinnabar-bear ing ores and flotation concentrates. Leaching time and solution temperature had minor effects on mercury extraction when compared to the effects of reagent quantity and ore type and grade. Cinnabar, although readily soluble in sodium sulfide, was only partially soluble in potassium sulfide and essentially insoluble in ammonium sulfide. A double leach process was developed to extract selectively the arsenic from Hg-As products with K2S and to treat the residue with sodium sulfide-hydroxide solutions to extract the mercury.&apos; Mercury was then recovered from the pregnant solutions either by precipitation with metallic aluminum or by electrodeposition. The solubility of HgS in alkaline sulfide solutions was first reported by Volhard in 1878.&apos; The first reported commercial application was made in 1915 when Thornhill applied the method to the treatment of an amalgamation tailing.3 Mullhollen, in 1911. described the chemical reaction of HgS with Na,S and alkaline hydrate to be:4 Most investigators have reported using a 4-pct sodium sulfide and a 1-pct sodium hydroxide soluti~n.3-4 An increase in temperature or excessive dilution of the solution causes the reaction to be reversed. Church Holmes described a similar process used for the extraction of antimony from silver concentrates at the Sunshine Mining Company&apos;s mill at Kellogg. Idaho.5 More recently. Erspamer and Wells reported the results of leaching studies on a Hg-Sb ore from Alaska.6 EXPERIMENTAL PROCEDURE Leaching tests were made on samples of mercury ore from eight deposits in Oregon, Washington, and Idaho. In addition. tests were made on flotation concentrates from seven of the samples as well as a flotation concentrate from an operating mill. Since previous investigators reported reagent requirements greatly in excess of that required by the equation HgS + Na2S = HgS . Na2S, initial studies were made on chemically pure HgS. Results showed that the reaction actually required about 1 g of Na,S per g of HgS in an aqueous solution rather than 0.338 g of Na,S as indicated by the equation. To check further the matter of reagent requirements, Na2S and HgS were mixed together in equal mole ratios. Water was then added, a drop at a time, until the components reacted; X-ray diffraction analyses showed no HgS nor Na,S present. The yellow hydrate compound which formed would not redissolve until about three additional mole equivalents of Na,S were added to the solution. This indicated that a stable solution would require at least 4 moles of Na2S for each mole of HgS. While these implications may be valid for pure HgS, the possibility of entirely different results caused by the existence of other elements present in ores and concentrates was recognized. Consequently, experiments of the same order were made on samples of a flotation concentrate from a producing mill. The concentrate, containing about 18 pct

Jan 1, 1962